CN109360960A - A kind of compound sulfur materials of CuCo bimetallic organic frame and its preparation and use - Google Patents
A kind of compound sulfur materials of CuCo bimetallic organic frame and its preparation and use Download PDFInfo
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Abstract
The invention discloses a kind of compound sulfur materials of CuCo bimetallic organic frame, it can be used as lithium sulfur battery anode material, the Cu atom and polarity Co atom not being coordinated completely are staggered in different proportions and form a kind of polyhedron-shaped MOF structure with organoligand coordination, sulphur and its reaction product polysulfide are present among the duct of the MOF structure, it adsorbs in the different activities site provided by duct and two kinds of metallic atoms, sulphur can be particularly well adsorbed in the duct of MOF by the structure, will not largely be lost because of the temperature of carbonization and the progress of reaction.The present invention also provides preparation methods, the present invention solves the problems, such as that lithium-sulfur cell capacity attenuation in charge and discharge process is too fast and positive electrode structural instability because of caused by volume expansion, and preparation method is simple, raw material is easy to get, advantageously account for the too fast problem of lithium-sulfur cell capacity attenuation, to accelerate the development of lithium-sulfur cell to a greater extent, there is very big researching value and commercial value.
Description
Technical field
The invention belongs to field of material technology, are related to lithium sulfur battery anode material, in particular to a kind of CuCo bimetallic has
The compound sulfur materials of machine frame and its preparation and use.
Background technique
Since the theoretical capacity of lithium ion battery is lower, there are more and more researchers to turn one's attention to lithium sulphur electricity
Pond.Lithium-sulfur cell is favored because of its higher theoretical capacity and energy density.Its theoretical specific capacity and energy density point
1675mAh/g and 2600Wh/kg are not can achieve.
Elemental sulfur is abundant and cheap in the storage capacity of nature, is can be very good as lithium-sulphur cell positive electrode in itself
Material.But the electric conductivity of elemental sulfur is too poor, electronic conductivity only has 5x10-30S.cm-1, this affects lithium to a certain extent
The development of sulphur battery.The reason of another restriction lithium-sulfur cell development is exactly the more lithium sulfides of reaction product in charge and discharge process
Dissolution and because its dissolution caused by shuttle effect, this is the master for causing lithium-sulfur cell capacity attenuation in charge and discharge process
Want reason.Usually we do used in method be by cladding carbon material come inhibit sulphur dissolution reduce capacity decaying and
To enhance the electric conductivity of positive electrode.
In recent years, unique suction of the MOF (metal organic frame, hereinafter referred to as MOF) because of the diversity and structure of its type
The sight of numerous lithium-sulfur cell researchers is drawn.MOF is mutually to be coordinated with other organic ligands by central metal atom and formed, it
Structure in containing there are three types of different size of duct 3 be macropore respectively, mesoporous and micropore, wherein the aperture of micropore it is smaller can will
Small more vulcanization lithium dimers are limited in inside its duct.It is mesoporous other than it can limit more lithium sulfides, it can also for reaction
Process intermediate ion and electronics provide transmission channel.
MOF has very big advantage as lithium-sulphur cell positive electrode carrier material.That is reported in recent years makees lithium-sulfur cell
Most of in the MOF structure of positive electrode is all monatomic MOF structure.For example, HKUST-1, ZIF-8, ZIF-67, MOF-5 system
Column.It is single but since monometallic atom can not preferably solve the dissolution of the loss and polysulfide of sulphur in charge and discharge process
Application of the MOF structure of atom on lithium-sulfur cell has been in bottleneck period.In this regard, R and D, which go out, is more advantageous to maintenance lithium
The MOF structure of sulphur battery capacity has been extremely urgent work.
Summary of the invention
The disadvantages of in order to overcome above-mentioned prior art lithium-sulfur cell capacity attenuation too fast, the purpose of the present invention is to provide one
Sulphur can be particularly well adsorbed in MOF's by the compound sulfur materials of kind CuCo bimetallic organic frame and its preparation and use, the structure
In duct, will not largely it be lost because of the temperature of carbonization and the progress of reaction.MOF (CuCo)-S is bimetallic MOF structure borne
Pass through the obtained combination product of high temperature cabonization after sulphur.The compound solves lithium-sulfur cell capacity in charge and discharge process and declines
Subtract too fast and positive electrode because of caused by volume expansion the problem of structural instability.In addition to this, it is carried out before carbonization
Carry sulphur, sulphur simple substance can be made to combine before redox reaction occurs with this new structural MOF, formation chemical bond from
And reduce the loss of sulphur.Inhibiting effect all is played to the dissolution of polysulfide before and after discharge and recharge reaction.Furthermore carbonization can be with
Enhance the electric conductivity and specific surface area of compound.The structure preparation method is simple, and raw material is easy to get, and advantageously accounts for lithium-sulfur cell appearance
The too fast problem of amount decaying has very big researching value and business to accelerate the development of lithium-sulfur cell to a greater extent
Value.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of compound sulfur materials of CuCo bimetallic organic frame, the Cu atom not being coordinated completely and polarity Co atom be not with
Same ratio is staggered and forms a kind of polyhedron-shaped MOF structure, sulphur and its reaction product with organoligand coordination
Polysulfide is present among the duct of the MOF structure, the different activities site institute provided by duct and two kinds of metallic atoms
Absorption.
In the MOF structure, Cu and Co exist according to the distinct interaction of content, and the content of Cu and Co are by Cu (NO3)2·
3H2O and Co (NO3)2·6H2The different proportion of O determines.Wherein, Ni metal organic ligand H corresponding with it3NTB and DABCO
Coordination mode be not exclusively to be coordinated, the coordination mode of Co metal organic ligand 2-methylimidazole corresponding with it is to match completely
Position.
The present invention also provides the preparation methods of the compound sulfur materials of CuCo bimetallic organic frame, and steps are as follows:
Firstly, the CuCo bimetallic MOF being not exclusively coordinated by Cu salt, Co salt, organic ligand and corresponding solvent
Crystal；
Then, the CuCo bimetallic MOF-S compound being not exclusively coordinated in tube furnace by melting diffusion method；
Finally, enhancing the electric conductivity and specific surface area of compound by being carbonized.
The preparation process of the bimetallic MOF crystal is as follows:
Take metal salt Cu (NO3)2·3H2O and Co (NO3)2·6H2Three kinds of organic ligand H are added in O3NTB, DABCO and 2-
The solvent of methylimidazole, addition is DMA, DMSO, fluoboric acid, Isosorbide-5-Nitrae-dioxane, ethyl alcohol and methanol, is stirred after mixing by magnetic force
It mixes or is ultrasonically treated and obtain uniformly mixed solution, the CuCo bimetallic MOF crystal being not exclusively coordinated is made.
Cu (the NO3)2Dosage is 0.035~0.040g, Co (NO3)26H2O dosage is 0.012~0.040g, H3NTB is used
Amount is 0.02~0.05g, and DABCO dosage is 0.02~0.05g, and 2-methylimidazole dosage is 0.040~0.052g, DMA dosage
For 2~6mL, DMSO dosage is 1~3mL, and fluoboric acid dosage is 0.05~0.25mL, and Isosorbide-5-Nitrae do dosage is 0.5mL~1.5mL, second
Alcohol dosage is 1~5mL, and methanol usage is 8~12mL, and the time of magnetic agitation or ultrasonic treatment is 25~35min.
The CuCo that the present invention can be not exclusively coordinated by the method for solvent heat in solvent-thermal method, hydro-thermal method or oil bath pan
Bimetallic MOF crystal.
The preparation process of the CuCo bimetallic MOF-S compound is as follows:
By the CuCo bimetallic MOF crystal and simple substance sulphur powder according to mass ratio 2:(3~6) in the glove box for being full of argon gas
Middle mixed grinding, and be sintered at 150 DEG C~160 DEG C in tube furnace, it keeps the temperature, cooled to room temperature.
The carbonization is that the CuCo bimetallic MOF-S compound is put into tube furnace to be carbonized at high temperature, then certainly
It is taken out after being so cooled to room temperature, the carbon derivative for the CuCo bimetallic MOF being not exclusively coordinated, the temperature being carbonized in tube furnace
It is 400~800 degree, soaking time is 2~4h, and heating rate is 3 DEG C~5 DEG C.
The gained compound sulfur materials of CuCo bimetallic organic frame of the invention can be used as lithium sulfur battery anode material.In charge and discharge
In the process, with the sulphur simple substance of anode redox reaction can occur for the lithium ion of cathode, and Li can be generated in the reaction process2S8、
Li2S6And Li2S4It is soluble in the lithium sulfide of electrolyte, the dissolution of these polysulfides in the electrolytic solution will cause battery appearance
The decaying of amount, and because the difference of their own density will cause the dusting of cathode material structure, influence the stability of material.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention is a kind of completely new CuCo bimetallic MOF structure, its unique organic ligand and solvent determine certainly
The coordination mode of body stable structure and central metal.The presence of this rock-steady structure ensure that positive electrode knot in cyclic process
The stabilization of structure.
(2) CuCo novel dual metal MOF structure, the lewis acid activity position that the Cu metallic atom being not exclusively coordinated is provided
The suction-operated of point, polar metal Co add itself duct of MOF structure to more vulcanizations to the chemisorption of polarity
The inhibiting effect triplicity of object dissolution is got up, and slows down the rate of decay of capacity to a greater extent.
(3) first that bimetallic MOF and sulphur simple substance is compound during preparing MOF (Cu, Co)-S compound, and then
It is carbonized to it.The active site that bimetallic MOF can be made to provide is when sulphur has neither part nor lot in redox reaction just first by it
Absorption, controls the loss of sulphur, and due to the strong suction-operated for sulphur of this novel MOF structure, high temperature cabonization will not
Influence content of the sulphur in the duct MOF.To inhibit the dissolution of polysulfide in itself, the circulation of lithium-sulfur cell is increased
Service life.
(4) the MOF structure possesses unique biggish meso-hole structure, is adapted to due to reaction product density is different
Caused volume expansion prevents the dusting of cathode material structure.
Detailed description of the invention
Fig. 1 is Cu-Co bimetallic MOF structural schematic diagram of the present invention.
Fig. 2 is that three kinds of MOF structures of the invention recycle 20 discharge capacity decay patterns under 0.5C multiplying power.
Fig. 3 is first charge-discharge curve graph of the three kinds of MOF structures of the invention under 1C multiplying power.Wherein, (a) is bimetallic
MOF (Cu-Co) -- S first charge-discharge curve is (b) MOF (Cu) -- S first charge-discharge curve is (c) that MOF (Co) -- S is for the first time
Charging and discharging curve.
Specific embodiment
The embodiment that the present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1:
Step 1: the Cu (NO of 0.035g is weighed3)3H2The H of O, 0.02g3The DABCO of NTB, 0.02g are as metal salt and have
1mL ethyl alcohol, 3mLDMA, 1mLDMSO, 0.1mL fluoboric acid and 1mL1,4-do is added in machine ligand into said mixture respectively.It will
Acquired solution magnetic agitation is until solution is put into drying box at 85 DEG C 5-7 days dry, resulting ink after taking-up after mixing
Green crystal is using Cu as the MOF crystal of center metallic atom.
Step 2: by MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the glove box full of argon gas
Ground and mixed.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cool to room
It is taken out after temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature and obtains final product MOF
(Cu)-S compound.
Embodiment 2:
Step 1: the Co (NO of 0.036g is weighed3)26H2O is dissolved in 5mL methanol solution, and the 2-methylimidazole of 0.047g is molten
It in 5mL methanol solution, is placed on magnetic stirrer after the two is mixed and stirs 30min, after standing for 24 hours, acquired solution is passed through
Purple precipitating is obtained by filtration in washing, is then placed in drying box under 70 degree overnight, obtains the MOF crystal using Co as center atom.
Step 2: by MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the glove box full of argon gas
Ground and mixed.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, and soaking time is that 2h naturally cools to room
It is taken out after temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature and obtains final product MOF
(Co)-S compound.
Embodiment 3:
Step 1: 0.036gCu (NO is weighed according to the ratio of 1:13)3H2O and 0.036g Co (NO3)26H2O is as metal
Salt is added in vial, weighs 0.02gH3NTB, 0.02g DABCO and 0.045g 2-methylimidazole as organic ligand,
Dropwise addition 3mLDMA, 1mLDMSO, 1mL ethyl alcohol, 0.1mL fluoboric acid, 1mL1,4do and 8mL methanol in mixture is stated then up.It will
Above-mentioned solution is put into stirring on magnetic stirrer until being uniformly mixed, and is then placed in drying box at 85 DEG C 5-7 days dry.It takes out
After obtain bimetallic MOF crystal structure.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Cu, Co)-S compound.
Embodiment 4:
Step 1: the Cu (NO of 0.035g is weighed3)3H2The H of O, 0.02g3The DABCO of NTB, 0.02g are as metal salt and have
1mL ethyl alcohol, 3mLDMA, 1mLDMSO, 0.1mL fluoboric acid and 1mL1,4-do is added in machine ligand into said mixture respectively.It will
Acquired solution magnetic agitation is until solution is put into drying box at 85 DEG C 5-7 days dry, resulting ink after taking-up after mixing
Green crystal is using Cu as the MOF crystal of center metallic atom.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Cu)-S compound.
Embodiment 5:
Step 1: 0.018 Co (NO is weighed3)26H2O is dissolved in 4mL methanol solution, and the 2-methylimidazole of 0.047g is dissolved in
It in 4mL methanol solution, is placed on magnetic stirrer after the two is mixed and stirs 30min, after standing for 24 hours, by acquired solution through washing
It washs, purple precipitating is obtained by filtration, be then placed in drying box under 70 degree overnight, obtain the MOF crystal using Co as center atom.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Co)-S compound.
Embodiment 6:
Step 1: 0.036g Cu (NO is weighed according to the ratio of 2:13)3H2O and 0.018g Co (NO3)26H2O is as metal
Salt is added in vial, weighs 0.02g H3NTB, 0.02g DABCO and 0.040g 2-methylimidazole are organic ligand,
Dropwise addition 3mLDMA, 1mLDMSO, 1mL ethyl alcohol, 0.1mL fluoboric acid, 1mL1,4do and 8mL methanol in mixture is stated then up.It will
Above-mentioned solution is put into stirring on magnetic stirrer until being uniformly mixed, and is then placed in drying box at 85 DEG C 5-7 days dry.It takes out
After obtain bimetallic MOF crystal structure.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Cu, Co)-S compound.
Embodiment 7:
Step 1: the Cu (NO of 0.035g is weighed3)3H2The H of O, 0.02g3The DABCO of NTB, 0.02g are as metal salt and have
1mL ethyl alcohol, 3mLDMA, 1mLDMSO, 0.1mL fluoboric acid and 1mL1,4-do is added in machine ligand into said mixture respectively.It will
Acquired solution magnetic agitation is until solution is put into drying box at 85 DEG C 5-7 days dry, resulting ink after taking-up after mixing
Green crystal is using Cu as the MOF crystal of center metallic atom.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Cu)-S compound.
Embodiment 8:
Step 1: the Co (NO of 0.012g is weighed3)26H2O is dissolved in 3mL methanol solution, and the 2-methylimidazole of 0.047g is molten
It in 3mL methanol solution, is placed on magnetic stirrer after the two is mixed and stirs 30min, after standing for 24 hours, acquired solution is passed through
Purple precipitating is obtained by filtration in washing, is then placed in drying box under 70 degree overnight, obtains the MOF crystal using Co as center atom.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Co)-S compound.
Embodiment 9:
Step 1: 0.036g Cu (NO is weighed according to the ratio of 3:13)3H2O and 0.012g Co (NO3)26H2O is as metal
Salt is added in vial, weighs 0.02g H3NTB, 0.02g DABCO and 0.040g 2-methylimidazole are matched as organic
Body states dropwise addition 3mLDMA, 1mLDMSO, 1mL ethyl alcohol, 0.1mL fluoboric acid, 1mL1,4do and 8mL first in mixture then up
Alcohol.Above-mentioned solution is put into stirring on magnetic stirrer until being uniformly mixed, is then placed in drying box at 85 DEG C dry 5-7
It.Bimetallic MOF crystal structure is obtained after taking-up.
Step 2: by bimetallic MOF crystal obtained above and simple substance sulphur powder according to the ratio of 2:3 in the hand for being full of argon gas
Ground and mixed in casing.It is sintered to be put into tube furnace after grinding completely, temperature is 155 degree, soaking time 2h.Naturally cold
But to taking out after room temperature.Obtain MOF-S compound.
Step 3: the MOF-S compound that step 2 obtains is put into tube furnace and is carbonized.In the tubular type for being full of argon gas
In furnace, carburizing temperature is set as 600 degree, soaking time 2h.It is taken out after cooled to room temperature, obtains final product MOF
(Cu, Co)-S compound.
The present invention combines the effects of two kinds of metals along with the absorption in the duct MOF inhibits polysulfide jointly
Dissolution, MOF structure is other than the duct of itself can inhibit the dissolution of polysulfide, central metal atom and organic ligand
It can also be good to inhibiting the dissolution of polysulfide to play the role of.Provided by some central metal atoms being not exclusively coordinated
Lewis acid activity site can form chemical bond with reaction product polysulfide to inhibit the decaying of capacity.Likewise, some
Polar metal is easier to form polarity Coordinative Chemistry key with reaction product, this can also limit the dissolution of polysulfide well.
When doing lithium sulfur battery anode material, MOF-S and acetylene black, PVDF mass ratio according to 5:3:2.Suitable NMP is added
Positive electrode slurries are prepared after solution by magnetic agitation 12h, slurries are coated on aluminium foil after the completion of stirring and are put into vacuum
It is dried under 60 degree in drying box, carries out cut-parts with slitter after the completion of dry and each pole piece is claimed using balance
Amount finally carries out the assembling of battery in the glove box full of argon gas.Phase is carried out to it after assembled battery is shelved 12h
The electro-chemical test answered carries out 50 loop tests of charge and discharge to the MOF of three kinds of structures, as shown in Figure 2 under 0.5C multiplying power.By
The rate of decay that Fig. 2 can be seen that bimetallic MOF capacity will be far smaller than other two kinds of MOF structures, recycle it by 50 times
The capacity that bimetallic MOF structure does positive electrode afterwards still can achieve 1000mAh/g or more, and the capacity of other two kinds of structures
Only less than 700mAh/g.Charge-discharge test is carried out under 1C multiplying power to the MOF of three kinds of structures, (a) (b) (c) is three kinds in Fig. 3
The MOF of structure first charge-discharge curve graph under 1C multiplying power.The discharge capacity for the first time of bimetallic MOF knot can achieve 1400mAh/
G, and the discharge capacity for the first time of other two kinds of structures only has 1000mAh/g.By the test of Fig. 2 and Fig. 3 it follows that bimetallic
Structure plays an important role during inhibiting lithium-sulfur cell capacity attenuation, its unique structure and corresponding metal position
Point all plays suction-operated to polysulfide, inhibits their dissolution to a greater extent.What is carried out under high magnification fills
Discharge cycles test, its discharge capacity for the first time are still maintained at 1400mAh/g, this is also adequately demonstrated by bimetallic MOF knot
The stability of structure charge and discharge under high magnification.
Schematically the present invention and embodiments thereof are described above, description is not limiting, institute in attached drawing
What is shown is also one of the embodiment of the invention.Actual structure is not limited only to this.
Claims (10)
1. a kind of compound sulfur materials of CuCo bimetallic organic frame, which is characterized in that the Cu atom and polarity not being coordinated completely
Co atom is staggered in different proportions and forms a kind of polyhedron-shaped MOF structure with organoligand coordination, sulphur and
Its reaction product polysulfide is present among the duct of the MOF structure, the difference provided by duct and two kinds of metallic atoms
Active site is adsorbed.
2. the compound sulfur materials of CuCo bimetallic organic frame according to claim 1, which is characterized in that in the MOF structure,
Cu and Co exists according to the distinct interaction of content, wherein the coordination mode of Cu metal organic ligand corresponding with it is incomplete
Coordination, the coordination mode of Co metal organic ligand corresponding with it are coordination completely.
3. the compound sulfur materials of CuCo bimetallic organic frame according to claim 1, which is characterized in that the Cu metal is corresponding
Organic ligand be H3The corresponding organic ligand of NTB and DABCO, Co metal is 2-methylimidazole.
4. a kind of preparation method of the compound sulfur materials of CuCo bimetallic organic frame, steps are as follows:
Firstly, the CuCo bimetallic MOF crystal being not exclusively coordinated by Cu salt, Co salt, organic ligand and corresponding solvent；
Then, the CuCo bimetallic MOF-S compound being not exclusively coordinated in tube furnace by melting diffusion method；
Finally, enhancing the electric conductivity and specific surface area of compound by being carbonized.
5. the preparation method of the compound sulfur materials of CuCo bimetallic organic frame according to claim 4, which is characterized in that described
The preparation process of bimetallic MOF crystal is as follows:
Take metal salt Cu (NO3)2·3H2O and Co (NO3)2·6H2Three kinds of organic ligand H are added in O3NTB, DABCO and 2- methyl miaow
Azoles, the solvent of addition are DMA, DMSO, fluoboric acid, Isosorbide-5-Nitrae-dioxane, ethyl alcohol and methanol, after mixing by magnetic agitation or
Ultrasonic treatment obtains uniformly mixed solution, and the CuCo bimetallic MOF crystal being not exclusively coordinated is made.
6. the preparation method of the compound sulfur materials of CuCo bimetallic organic frame according to claim 5, which is characterized in that described
Cu(NO3)2Dosage is 0.035~0.040g, Co (NO3)26H2O dosage is 0.012~0.040g, H3NTB dosage be 0.02~
0.05g, DABCO dosage are 0.02~0.05g, and 2-methylimidazole dosage is 0.040~0.052g, and DMA dosage is 2~6mL,
DMSO dosage is 1~3mL, and fluoboric acid dosage is 0.05~0.25mL, and Isosorbide-5-Nitrae do dosage is 0.5mL~1.5mL, ethanol consumption 1
~5mL, methanol usage are 8~12mL, and the time of magnetic agitation or ultrasonic treatment is 25~35min.
7. according to the preparation method of the compound sulfur materials of CuCo bimetallic organic frame of claim 5 or 6, which is characterized in that
The CuCo bimetallic MOF crystal being not exclusively coordinated by the method for solvent heat in solvent-thermal method, hydro-thermal method or oil bath pan.
8. the preparation method of the compound sulfur materials of CuCo bimetallic organic frame according to claim 4, which is characterized in that described
The preparation process of CuCo bimetallic MOF-S compound is as follows:
By the CuCo bimetallic MOF crystal and simple substance sulphur powder according to mass ratio 2:(3~6) it is mixed in the glove box full of argon gas
Grinding is closed, and is sintered at 150 DEG C~160 DEG C in tube furnace, is kept the temperature, cooled to room temperature.
9. the preparation method of the compound sulfur materials of CuCo bimetallic organic frame according to claim 4, which is characterized in that described
Carbonization is that the CuCo bimetallic MOF-S compound is put into tube furnace to be carbonized at high temperature, then cooled to room temperature
After take out, the carbon derivative for the CuCo bimetallic MOF being not exclusively coordinated, the temperature being carbonized in tube furnace is 400~800
Degree, soaking time are 2~4h, and heating rate is 3 DEG C~5 DEG C.
10. the purposes that the compound sulfur materials of CuCo bimetallic organic frame described in claim 1 are used as lithium sulfur battery anode material.
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